Quaternary ammonium compounds and method of producing the same



Patented Sept. 15, 1942 UNITED STATES PATENT OFFICE QUATERNARY AMMONIUMCOMPOUNDS AND METHOD OF PRODUCING THE SAME Winfrid Hentrich,Dusseldorf-Reisholz, Wilhelm Kaiser, Dessau in Anhalt, and Werner Reuss,deceased, late of Dusseldorf-Benrath, Germany, by Elfriede Reuss, widowand sole heir,

Dusseldorf Benrath, Germany;

Carl-Heinz No Drawing. Application April 8, 1938, Serial No.

5 Claims.

The present invention has for an object to provide an improvedquaternary ammonium compound and an improved method of producing thesame.

The producing of amino-carboxylic acid amides or -esters including thosewhich in the amideor in the ester group contain at least one lipophileradical, or residue, is not new. It can be performed in letting ammoniaor amines react upon halogenated carboxylic acid amides or ous compoundsare obtainable in converting such amino-carboxylic acid amides or-esters containing on the amino-nitrogen or in the ester group at leastone lipophile radical, into quaternary ammonium compounds.

The amino-carboxylic acid amides or -esters which may be applied asinitial stuifs for the present method, are of the general formulaR.R1.N.Rz.CO.X.R3. In this formula R and R1 mean hydrogen or anyhydrocarbon radicals which also conjointly may form with thenitrogen-atom a hetero-cyclic ring; R2 means a bi-valent hydrocarbonradical; X represents NR4(R4=hydrogen or any hydrocarbon radical) or 0,whilst R3 is to be a hydrocarbon radical with no less than 6 carbonatoms.

R and R1 may e. g. be formed of methyl-, ethyl-, propyl-, allyl-groupsand the like, or they may also belong to a piperidineor pyrrolidinering. The several compounds are similar and, to a substantial extent,equivalents in that they all have the important trivalent nitrogen atom.Further they may be formed of a benzyl-, furfuryl-radical and the like.R2 may be represented by e. g. an ethylene-, phenyl ethylene-,propyleneor butylene radical and the like. R3 may be formed of a highermolecular hydrocarbon radical containing no less than 6 C atoms of thealiphatic, cycle-aliphatic, aromatic and fatty aromatic series such as aheXyl-, octyl-, decyl-, dodecyl-, cetyl-, octadecyl-, octadecenyl-,hydroxy-octadecenyl radical and the like. Moreover B: may be representedby a cycloheXyl radical, an alkylated cyclohexyl radical such as thep-dodecyl-o-methyl-cyclohexyl radical, a naphthenyl radical, an abiethylradical, a phenyl radi- In Germany April 13, 1937 cal, an alkylatedphenyl radical, a benzyl radical and the like. Those radicals may alsocontain hetero-atoms and hetero-atom groups such as oxygen, sulfur,nitrogen and the like. R4 may be e. g. a radical of methyl, ethyl,propyl, allyl, butyl, benzyl, furfuryl, phenyl and the like.

Among the amino-carboxylic acid amides or -esters applicable as initialstuffs for the present invention there are to be considered e. g.dimethyl-amino-acetic acid-octyl-amide, piperidino-aceticacid-octyl-amide, dimethyl-amino-butyric acid-dodecyl-amide,dimethyl-amino-acetic acid-undecylene-amide, dimethyl-amino-aceticacid-dodecyl-amide, di-ethyl-amino-acetic acidcetyl-amide,,3-dimethyl-amino-u-diethyl-propionic acid-cetyl-ester,piperidino-acetic acid-dodecyl-benzyl-amide, dimethyl-amino-acetic acid-(p-dodecoxy) -phenyl-amide, and further the amino-aceticacid-dodecyl-amide, methyl-aminoacetic acid-cetyl ester, amino-propionicacid-dodecyl-benzyl amide and the like.

The converting of those compounds into quaternary ammonium compounds isaccomplished by direct reaction of mineral acid esters of aliphatic,fatty aromatic, cyclo-aliphatic or heterocyclic alcohols such asalkyl-halogenides, e. g. methy1- chloride, methyl-iodide, allyl-bromide,octylbromide, hexadecyl-bromide, further the dimethyl sulfate,diethyl-sulfate, octyl-mono-sulfuric acid ester, benzyl chloride,furfuryl chloride, tetra-hydro-furfuryl chloride and the like.

The conversion by reaction between the aminocarboxylic acid-amides or-esters,on the one hand, and the mineral acid esters, on the other hand,

' is performed while warming up and eventually in the presence ofsolvents or diluents.

Example 1 To 310 parts by weight of melted dodecyl-amide of thepiperidino-acetic acid 127 parts by weight of benzyl chloride are addedwhile stirring and at a temperature of 50 C. After warming up from 50 toC. until the reaction is at its end, one allows cooling, whereby themelt solidifies to a crystalline mass. The thus obtainedpiperidinoacetic acid-dodecyl-amide-chlorobenzylate dissolves clear inwater and the aqueous solution is much lathering. By re-crystallizingfrom xylol the product can be obtained quite colourless (melting point114 0.). A similar compound is obtained in warming 7 parts by weight ofpiperidino-acetic acid-dodecyl-benzyl amide up to 50- 60 C. for about 2hours together with 2,2 parts by weight of dimethyl-sulfate.

Example 2 19 parts by weight of piperidino-acetic aciddodecyl ester arewarmed up to 80-90 C. for 8 hours together with 13 parts by weight ofbenzylchloride. Then the mixture is dissolved in water and warmed,whereby the excess benzyl-chloride, which is floating in the form of oilon the surface of the solution, is to be separated off. Afterevaporating the solution liberated from the benzylchloride, we obtainthe piperidino-acetic aciddodecyl-ester-chlorobenzylate in the form of apowder. One may also substitute a mixture of fatty alcohol esters forthe dodecyl-ester.

Example 3 270 parts by weight of dimethyl-amino-aceticacid-dodecyl-amide are warmed up to 50-60" C. for several hours togetherwith 127 parts of benzyl-chloride. Thethus obtained crystalline mass mayeventually be ground with a solvent (decahydronaphthalin) f orpurification. By sucking oii the solvent we obtain thedimethylamino-acetic acid-dodecyl-amide-chlorobenzylate being a wellcrystallized substance (melting point 147 to 148 C.) soluble clear inwater. This compound may be described as N-dimethyl N-benzyl N-chlorN-methyl-dodecyl-glycinamide.

In a similar manner we obtain the dimethylamino-acetic acid (furfuryl-dodecyl amide)- chloromethylate, piperidino-acetic acid (l-sec.-octy1-2-methyl-cyclohexyl-methylamide) -chlorobenzylate,(benzyl-methyl-amino)-acetic acid- (methyl dodecyl amide)-chloromethylate, dimethyl-amino-acetic acid (benzyl-dodecyl-amide)-chloromethylate and the like.

Those quaternary ammonium compounds distinguish themselves, withoutcounting their water-solubility and indifference to hardnessprovokers ofthe Water and to hydrolysing influences, not only by an excellentsoap-like action, but also by a most remarkable disinfecting action upone. g. the staphylo-coccus and the typhus bacillus.

Those compounds offer moreover the advantage of being obtainable in agenerally very good crystalline form allowing an easy dosing and mixingwith substratums. Besides this we can without difficulty obtaincrystallizable products of such a purity as required e. g. forpharmaceutical purposes.

The aforesaid compounds may be applied either alone or mixed with otherdisinfecting media and eventually with an addition of diluents orstretching agents for the disinfection of commodities, medicalinstruments, textiles, linen, walls, tiles, floors, implements,apparatus used in the alimentary and appetizing products industry, aswell as for the disinfecting of animals and parts of the human body.Moreover they are apt for the preserving of perishable animal andvegetable goods such as pastes and sizes, furs, hides, skins and thelike.

The quaternary amino-carboxylic acid-amides of the present invention aree. g. of the general formula Am.R.CO.N.R"R/. In this formula R'.CO meansthe radical of an aliphatic acid such as acetic acid, propionic acid andbutyric acid, R"=hydrogen or any organic radical. R means a lipophileradical such as octyl-, nony1-, deoyl-, dodecyl-, tridecyl-,tetradecyl-, hexadecyl radical or the like. "Am represents any quatenaryammonium group containing anion. The ammonium group may contain equal ormixed aliphatic, aromatic, aliphatic-aromatic or heterocyclic radicals.0f a particularly good disinfecting power are those compounds, which inthe molecule e. g. in the quaternary ammonium group or on theamino-nitrogen contain an unsaturated hydrocarbon radical such as thebenzyl residue, the allyl-residue and the like.

The compounds of the present invention may therefore be applied alsowith alkaline or acid stuffs. Moreover they are of a good wettingpowerby which the penetration into textiles and the spreading-out on soiledand stained surfaces is considerably enhanced. The efliciency and themode of application of the compounds in question as disinfecting andpreserving agents is shown by the following examples:

(a) A 0.01% -solution of (benzyl -methylamino) -aceticacid-dodecylamide-chloromethylate of the formula (CH3) 2. (C'IH'Z)NC1.CH2.CO.NH.C12H25 kills completely, at 20 C. a deposit of mycodermawithin 15 minutes.

A 0.002%-solution of the same compound destroys completely at 20 C. adeposit of bacteria coli within 45 minutes.

A 0.0057%-solution of the same compound destroys completely, at 20 C., adeposit of staphylococcus aureus within 5 minutes.

Of a similar efiiciency are also the compounds where the dodecyl-radicalis replaced by an octyl-, decylor tetra-decyl radical, as well as themixtures of those bodies.

(b) A 0.01%-solution of dimethyl-amino-aceticacid-dodecylamide-chloromethylate of the formula (C113)3.NC1.CH2CO.NH.C12H25 kills, at 20 C., a deposit of bacteria colicompletely within 15 minutes. This compound may be described asN-trimethyl N-chlor N'-dodecyl-glycinamide.

A 0.014%-solution of the same compound destroys completely, at 20 C., adeposit of pyocyaneus within 5 minutes.

(0) A 0.005%-solution of dimethyl-aminoacetic acid(benzyl-dodecyl-amide)-chloromethylate of the formula (CI-I3)3.NC1.CH2.CO.N(C7H7) (CHI-) kills completely a deposit of bacteria coliwithin 15 minutes. This compound may be described as N-trimethyl N-chlorN-benzyl N' -dodecyl-glycinamide.

The same efficiency shows a 0.005%-solution of piperidino-aceticacid-dodecylamide-chloromethylate of the formula (d) The 1%--solution ofa mixture of '70 parts by weight of crystallized sodium-meta-silicate,29 parts of crystallized tri-basic sodium-phosphate and 1 part of thedimethyl-amino-acetic aciddodecyl-amide-chloromethylate mentioned inexample (b), kills completely, at 50 C., a deposit of mycoderma within 5minutes. This solution may be heated for a rather long time and kept forseveral days without reducing its disinfecting power.

(e) A 0.005%-solution of (benzyl methylamino) -acetic acid-(methyldodecyl amide) chloromethylate of the formula kills completely, at 20C., a deposit of bacteria coli within 30 minutes. This compound may bedescribed as N-dimethyl N-benzyl N-chlor-dodecylglycinamide.

(f) A 0.01%-so1ution of dimethyl aminophenyl-acetic acid dodecyl-amidechloromethylate of the formula (CH3) 3.NC1.CH. (CeHs) CO.NH.C12H25destroys entirely, at 20 C., a deposit of bacteria coli within 15minutes.

(g) A 0.002%-solution of benzyl-cyclohexylamino-aceticacid-dodecylamide-chloromethylate of the formula kills completely, at 20C., a deposit of bacteria coli within 45 minutes. This compound may bedescribed as N-methyl N-benzyl N-cyclohexyl N-chlorN'-dodecyl-glycinamide.

(h) 40 parts by weight of caustic soda, 30 of sodium-meta-silicate ofthe formula 19 parts by weight of calcined tri-sodium-phosphate, 10 ofsoda ash and 1 part of piperidinoaceticacid-dodecylamide-chlorobenzylate (or N- pentamethyl N-benzylN-chlor-dodecyl-glycin amide) of the formula are well mixed together. Anaqueous solution of this mixture at the ratio of 0.25% kills entirely,at 50 C., a deposit of bacteria coli within 6 minutes.

The aqueous solutions of this mixture may be applied as excellentdetergents of a simultaneous disinfecting action.

We claim:

1. A quaternary ammonium compound of the general formulaR.R1.R5.N.Y.R2.CO.NH.R3 in which R1 and R2 each represent a member ofthe group consisting of hydrogen and the hydrocarbon radicals containing1 to 3 carbon atoms, R5 represents a hydrocarbon radical, Y represents amineral acid radical, R2 represents an alkylene group containing 2 to 4carbon atoms and R3 represents a hydrocarbon radical containing 6 to 18carbon atoms.

2. The quaternary ammonium compound N- dimethyl N-benzyl N-chlorN-dodecyl-glycinamide.

3. The method of manufacturing nitrogenous compounds characterized byreacting compounds of the general formula R.R1.N.R2.CO.NH.R3, in which Rand R1 each represent a member of the group consisting of hydrogen andthe hydrocarbon radicals containing 1 to 3 carbon atoms, R2 represents ahydrocarbon radical, containing 2 to 4 carbon atoms, and R3 representsan alkyl radical containing 6 to 18 carbon atoms, with mineral acidesters of alcohols to form quaternary ammonium compounds by addition ofthe component radicals of the mineral acid esters on the first N atom.

4. The method of manufacturing nitrogenous compounds characterized byreacting compounds of the general formula R.R1.N.R2.CO.NH.R3, in which Rand R1 each represent a member of the group consisting of hydrogen andthe hydrocarbon radicals containing 1 to 3 carbon atoms, R2 represents ahydrocarbon radical, containing 2 to 4 carbon atoms, and R3 representsan alkyl radical containing 6 to 18 carbon atoms, with mineral acidesters of the group consisting of methylchloride, methyl-iodide,allyl-bromide, octylbromide, hexadecyl-bromide, dimethyl-sulfate,diethyl-sulfate, and octyl-mono-sulfate, to form quaternary ammoniumcompounds by addition of the component radicals of the mineral acidesters on the first N atom. I n

5. The method of manufacturing nitrogenous compounds characterized byreacting compounds of the group consisting of dimethyl-amino-aceticacid-octyl-amide, tetramethyl-acetic acid-octylamide,dimethyl-amino-butyric acid-dodecylamide, dimethyl-amino-aceticacid-undecyleneamide, dimethyl-amino-acetic acid-dodecyl-amide,di-ethyl-amino-acetic acid-cetyl amide, and amino-aceticacid-dodecyl-amide, with mineral acid esters of the aliphatic alcoholsto form quaternary ammonium compounds by addition of the componentradicals of the mineral acid esters on the first N atom.

WINFRID HENTRICH.

WILHELM KAISER.

ELFRIEDE REUSS, Widow of Werner Reuss, Deceased.

